WO2024112745A1 - Procédé de production de thiosulfate d'ammonium à partir de digestat anaérobie - Google Patents

Procédé de production de thiosulfate d'ammonium à partir de digestat anaérobie Download PDF

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Publication number
WO2024112745A1
WO2024112745A1 PCT/US2023/080674 US2023080674W WO2024112745A1 WO 2024112745 A1 WO2024112745 A1 WO 2024112745A1 US 2023080674 W US2023080674 W US 2023080674W WO 2024112745 A1 WO2024112745 A1 WO 2024112745A1
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WIPO (PCT)
Prior art keywords
column
biogas
stream
process according
hydrogen sulfide
Prior art date
Application number
PCT/US2023/080674
Other languages
English (en)
Inventor
Michael J. RAY
Michael F. Ray
Matthew F. RAY
Original Assignee
ThioSolv, LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ThioSolv, LLC filed Critical ThioSolv, LLC
Publication of WO2024112745A1 publication Critical patent/WO2024112745A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/64—Thiosulfates; Dithionites; Polythionates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/006—Waste from chemical processing of material, e.g. diestillation, roasting, cooking
    • C05F5/008—Waste from biochemical processing of material, e.g. fermentation, breweries
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/05—Biogas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to a process for producing ammonium thiosulfate from anaerobic digestate. Specifically, the present invention removes hydrogen sulfide from anaerobic digestate and biogas while producing ammonium thiosulfate, a high value-added agricultural product.
  • anaerobic digesters are commonly employed to produce a natural gas that can be used as a fuel source.
  • This natural gas commonly referred to as biogas
  • the gas typically contains, but is not limited to, carbon dioxide, methane, ammonia, and hydrogen sulfide.
  • hydrogen sulfide is a highly toxic and corrosive gas that can be lethal to humans at low exposure limits.
  • Biogas with higher amounts of hydrogen sulfide than is permitted by environmental regulators must be removed by downstream processes.
  • ammonia is harmful at elevated levels and requires additional processing or removal prior to the recycling or storage of the anaerobic digestate.
  • ammonia or hydrogen sulfide may be entrained in the solution.
  • these gases may be uncontrollably released when applied to the soil, during blending with other components before application to the soil, upon contact with low pH materials in the soil, or during mixing with more acidic solutions.
  • the uncontrolled release of ammonia and hydrogen sulfide may cause serious harm to farmers, agricultural workers, or other individuals in the vicinity.
  • ammonia removal from digestate involves using air or steam. However, for small streams of digestate, this may not be a practical solution as the capital and operational expenditures may be large.
  • a process for producing ammonium thiosulfate (ATS) from anaerobic digestate and biogas involves reacting ammonia and hydrogen sulfide with sulfur dioxide.
  • ATS can be beneficially used as a slow- release agricultural fertilizer.
  • the process further involves substantially removing hydrogen sulfide and ammonia from the biogas.
  • the sulfur dioxide is replaced by ammonium bisulfite.
  • a process for producing ammonium thiosulfate from anaerobic digestate involves: routing a stream of the anaerobic digestate into a column with a circulating aqueous solution, wherein the anaerobic digestate stream comprises hydrogen sulfide; introducing a stream of sulfur dioxide into the column, wherein the sulfur dioxide reacts with the anaerobic digestate to produce an ammonium sulfite and/or ammonium bisulfite solution; routing a stream of biogas into the column, wherein the biogas comprises hydrogen sulfide; and contacting the hydrogen sulfide in the anaerobic digestate and the biogas stream with the ammonium sulfite and/or ammonium bisulfite solution to produce an effluent stream containing aqueous ammonium thiosulfate.
  • the column comprises a plurality contact zones.
  • the anaerobic digestate can be filtered prior to introduction into the column to substantially
  • the process further involves introducing an optional ammonia stream into the column.
  • the ammonia stream can be adjusted to maintain the pH in the column.
  • the pH can be balanced to a range of 5.5 to 8.5.
  • the biogas is produced from an anaerobic digestion reaction.
  • the biogas comprises methane, carbon dioxide, hydrogen sulfide, and ammonia.
  • the process further comprises substantially scrubbing the hydrogen sulfide from the biogas.
  • the scrubbed biogas/sweet biogas exits from the top of the column while the aqueous ammonium thiosulfate exits from the bottom of the column.
  • the sulfur dioxide can be introduced into the column at a first feed point, and the biogas can be routed to the column at a second feed point.
  • the second feed point can be located below the first feed point.
  • the sulfur dioxide stream can be substantially mixed with the anaerobic digestate prior to introduction to the column.
  • a portion of the aqueous ammonium thiosulfate can be recirculated back through the column depending on the concentration of the hydrogen sulfide in the biogas.
  • an ammonium bisulfite solution can be introduced to the digestate. Hydrogen sulfide in the anaerobic digestate and a biogas stream is contacted with the ammonium bisulfite solution to produce an effluent stream containing aqueous ammonium thiosulfate.
  • an ammonia stream can also be introduced into the column to maintain the pH in the column and balance stoichiometry. The pH is balanced to a range of 6.0 to 7.5.
  • a portion of the aqueous ammonium thiosulfate can be recirculated back through the column.
  • the process further comprises substantially scrubbing the hydrogen sulfide from the biogas.
  • the scrubbed biogas/sweet biogas exits from the top of the column while the aqueous ammonium thiosulfate exits from the bottom of the column.
  • FIG. 1 illustrates a schematic diagram of an exemplary system for reacting the ammonia and hydrogen sulfide from anaerobic digestate to create ammonium thiosulfate.
  • FIG. 2 illustrates a schematic diagram of an alternative system for reacting the ammonia and hydrogen sulfide from anaerobic digestate to create ammonium thiosulfate.
  • the terms “column” and “contact zone” can include any combination of towers, columns, trays, vessels, pumps, valves, control systems, and any other equipment known in the art useful in contacting liquids and gases.
  • the present invention relates to systems and processes for removing hydrogen sulfide and ammonia from a liquid or gas stream.
  • the present invention relates to a system for removing hydrogen sulfide and ammonia from anaerobic digestate and biogas to produce an agricultural fertilizer, such as ammonium thiosulfate (ATS).
  • ATS ammonium thiosulfate
  • anaerobic digestate from a digester is substantially contacted with sulfur dioxide at the top of a column.
  • the sulfur dioxide reacts with ammonia and water in the digestate to produce a mixture of ammonium bisulfite (ABS) and/or ammonium sulfite in the aqueous solution.
  • ABS ammonium bisulfite
  • the sulfite/bi sulfite solution further reacts with entrained hydrogen sulfide in the digestate to produce ammonium thiosulfate (ATS).
  • ATS ammonium thiosulfate
  • the flow of sulfur dioxide is controlled to maintain the pH of the solution to be between in a range that substantially captures hydrogen sulfide.
  • Biogas comprising carbon dioxide, methane, ammonia, and hydrogen sulfide from an anaerobic digester is added directly to the bottom of a column.
  • the biogas encounters the aqueous ABS/sulfite solution in one or more contact zones in the column whereupon hydrogen sulfide contained in the biogas reacts to form ammonium thiosulfate.
  • the ammonium thiosulfate stabilizes the remaining sulfite and bisulfite anions to inhibit further oxidation.
  • Excess sulfur dioxide is added to the anaerobic digestate to produce excess sulfite and bisulfite anions.
  • the additional sulfite anions ensure that hydrogen sulfide is substantially removed from the biogas when they are mixed.
  • excess ammonia can be added to the anaerobic digestate to balance the pH of the solution or to increase the amount of ATS in circulating solution.
  • ammonium thiosulfate solution exits the bottom of the column and is taken as a high value product or is recycled back to the top of the column to further react with biogas and anaerobic digestate. Continued recycling of the solution can be used to increase the amount of ATS in the final product.
  • the biogas exiting the top of the column can be substantially free of ammonia and hydrogen sulfide while the remaining components, carbon dioxide and methane, are unreacted.
  • a first process stream 10 containing digester feed can be introduced to Anaerobic Digester 100.
  • Liquid digestate from the Anaerobic Digester 100 can be transferred via process stream 20 to a top of Column 200.
  • the liquid digestate in stream 20 can be filtered to remove organic compounds or other impurities with the exception of the entrained ammonia and hydrogen sulfide.
  • the filtering process can be accomplished with any filter or media known in the art that substantially removes insoluble solids from a liquid stream.
  • the filtering of stream 20 further removes heavy metals, if present, prior to downstream processing.
  • a device such as a Venturi contactor can be used to substantially mix the digestate liquid and the sulfur dioxide gas prior to entering Column 200.
  • the digestate liquid and the sulfur dioxide gas can be mixed with any static mixer or other mixer known in the art.
  • Ammonia contained within the liquid digestate reacts with the sulfur dioxide to create ammonium bisulfite and/or ammonium sulfite.
  • the sulfite/bi sulfite solution can further react with entrained hydrogen sulfide to produce ammonium thiosulfate.
  • the embodiments of the invention facilitate removal of ammonia and hydrogen sulfide from the digestate.
  • the sulfur dioxide stream 25 can be obtained from the oxidation of sulfur on site, or it can be a purchased stream of sulfur dioxide.
  • an ammonium bisulfite solution can be utilized in place of sulfur dioxide gas as process stream 25.
  • the bisulfite solution is preferable for high concentrations of hydrogen sulfide entrained in the biogas wherein the stoichiometric ratio to sulfur to ammonia is also high.
  • the bisulfite solution can be introduced directly to the liquid digestate prior to entering the contact zone with the biogas.
  • a process stream 27 comprising aqueous or anhydrous ammonia, can be optionally added to one or more contact zones within Column 200.
  • the ammonia stream 27 can be utilized to adjust the pH or to balance the stoichiometry of the conversion of hydrogen sulfide in the system to ATS. It is understandable that the number of contact zones in Column 200 and the point at which process stream 27 is applied to the column is dependent on the phase of the ammonia source.
  • Biogas generated during digestion in Anaerobic Digester 100 proceeds through process stream 15 to Column 200.
  • the sulfur dioxide stream enters Column 200 above the biogas feed point allowing the digestate to contact the biogas.
  • the biogas is passed through the bottom of Column 200 where it flows upwards and contacts the liquid digestate. Excess sulfur dioxide gas added to the digestate in Column 200 produces excess sulfite anions in solution. The sulfites will subsequently react with hydrogen sulfide contained in the biogas to produce ammonium thiosulfate.
  • the pH in Column 200 is maintained between 5.5 and 8.5, and preferably between 6.0 and 7.5, by controlling the flow of sulfur dioxide and ammonia. It should be easily understandable to persons skilled in the art that the amount of sulfur dioxide and ammonia added, and the resulting pH can be optimized for the capture of hydrogen sulfide from the biogas and anaerobic digestate.
  • Biogas exiting from the top of Column 200 via stream 45 is substantially free of hydrogen sulfide (sweet biogas).
  • a liquid product containing ammonium thiosulfate leaves the bottom of Column 200 through process stream 30.
  • the liquid product may be recirculated or recycled via stream 35 back to the top of Column 200. Otherwise, the liquid product can be removed as process stream 40.
  • FIG. 2 an alternative embodiment of the process for producing ammonium thiosulfate from anaerobic digestate is shown. This is similar to the embodiment of FIG. 1 but does not include an additional ammonia process stream.
  • the embodiments of the present invention react the ammonia contained in the digestate to a bisulfite or ATS mixture, lower the vapor pressure of the ammonia in the liquid, and facilitates scrubbing the hydrogen sulfide out of the biogas.
  • ATS is considered as a slow-release fertilizer that is a good source of sulfur.
  • ATS inhibits bacteria in the soil from conversion of ammonia to ammonium nitrate which can end up in ground water and maintains the usable form of sulfur in the root zone longer.
  • the one or more embodiments of the present invention do not involve the separation of ammonia from the digestate. Instead, the ammonia present in the digestate is reacted with sulfur dioxide for conversion to ammonium sulfite, and a portion of this can further react with hydrogen sulfide in the digestate and biogas to produce ATS.
  • the one or more embodiments of the present invention can be used to produce useful fertilizer (ATS) from small streams of digestate.
  • ATS useful fertilizer
  • fertilizers cannot be produced from such small streams since the capital and operational expenditures are not justifiable.
  • sulfur dioxide can be directly contacted with the digestate for ammonia conversion to ammonium sulfite and a portion of that further reacts with hydrogen sulfide to produce ATS, which can be used for agricultural purposes.
  • additional treatment is not required to remove hydrogen sulfide from the biogas to meet most pipeline specifications and no additional waste material is created that requires disposal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Biotechnology (AREA)
  • Botany (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention concerne un procédé de production de thiosulfate d'ammonium à partir de digestat anaérobie. Le procédé consiste à injecter du dioxyde de soufre ou du bisulfite d'ammonium dans une colonne contenant un digestat liquide et un biogaz pour produire une solution de sulfite. La solution de sulfite réagit en outre avec du sulfure d'hydrogène entraîné dans le biogaz et le digestat pour produire du thiosulfate d'ammonium et du biogaz doux commercialement souhaitables.
PCT/US2023/080674 2022-11-22 2023-11-21 Procédé de production de thiosulfate d'ammonium à partir de digestat anaérobie WO2024112745A1 (fr)

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US202263384738P 2022-11-22 2022-11-22
US63/384,738 2022-11-22

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WO2024112745A1 true WO2024112745A1 (fr) 2024-05-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN209397027U (zh) * 2018-11-15 2019-09-17 湖北大学 一种撬装式沼液净化利用装置
WO2020160998A1 (fr) * 2019-02-04 2020-08-13 Haldor Topsøe A/S Procédé de purification de biogaz lors de la production d'un engrais contenant du soufre
US20210331923A1 (en) * 2020-04-24 2021-10-28 Clarke Rajchel Engineering, LLC Process for treating a mixed feed of hydrogen sulfide gas and ammonia gas to produce ammonium thiosulfate and including methodology for emissions control
US20210370227A1 (en) * 2020-05-26 2021-12-02 ThioSolv, LLC Process for removal of sulfur dioxide and ammonia from a vent gas stream
US20230295055A1 (en) * 2022-03-17 2023-09-21 ThioSolv, LLC Process for producing fertilizer from a biogas stream

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN209397027U (zh) * 2018-11-15 2019-09-17 湖北大学 一种撬装式沼液净化利用装置
WO2020160998A1 (fr) * 2019-02-04 2020-08-13 Haldor Topsøe A/S Procédé de purification de biogaz lors de la production d'un engrais contenant du soufre
US20210331923A1 (en) * 2020-04-24 2021-10-28 Clarke Rajchel Engineering, LLC Process for treating a mixed feed of hydrogen sulfide gas and ammonia gas to produce ammonium thiosulfate and including methodology for emissions control
US20210370227A1 (en) * 2020-05-26 2021-12-02 ThioSolv, LLC Process for removal of sulfur dioxide and ammonia from a vent gas stream
US20230295055A1 (en) * 2022-03-17 2023-09-21 ThioSolv, LLC Process for producing fertilizer from a biogas stream

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